CN100402445C - Sewage treating method for chitin production process - Google Patents
Sewage treating method for chitin production process Download PDFInfo
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- CN100402445C CN100402445C CNB2005100499966A CN200510049996A CN100402445C CN 100402445 C CN100402445 C CN 100402445C CN B2005100499966 A CNB2005100499966 A CN B2005100499966A CN 200510049996 A CN200510049996 A CN 200510049996A CN 100402445 C CN100402445 C CN 100402445C
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The present invention discloses an environmental protection treatment method in the process of chitin production, which comprises the technological steps: pretreatment of raw materials, acid leaching treatment, alkali treatment, etc. The present invention is characterized in that in each treatment technological stage, the wastewater is treated in a treatment pool, and waste substances are recovered; the wastewater treated in each technological stage is recycled. The present invention has the advantages that the traditional end treatment method is changed into single sewage treatment in the technological stages; pollutants, such as albumen, grease, pigments, etc., in the alkali treatment waste liquid are removed in the alkali treatment technological stage; the pollutants do not enter the acid leaching technological state, and the cross pollution is avoided; useful substances in acid leaching waste liquid are recovered. The present invention solves the problem that the wastewater produced by traditional chitin can not be treated by a conventional biochemical method because of high COD value and high chlorine ion content. The comprehensive sewage discharge which can reach the standard can be realized, and the byproducts are recovered and effectively utilized. The wastewater treated in each technological stage is recycled, and the used freshwater can be greatly saved.
Description
Technical field
The present invention relates to a kind of chitinous production method, especially relate to the sewage water treatment method in a kind of chitin production process.
Background technology
Chitin (being also referred to as chitin) is a kind of range of application material very widely, all has important effect in every field such as food, medicine, chemical industry and agriculturals, present most of chitin production method is to be raw material with shrimp, crab shell etc., adopt acid-base method to carry out processing treatment, and the production method of a kind of snail chitin of introducing in No. 02120794.1 Chinese invention patent also is to adopt above-mentioned method basically.Common byproducts such as grease with amounts of protein, muriate and a great deal of produce in the chitinous production process, it is big to produce waste liquid and chroma in waste water, COD and BOD value are very high, need handle factory effluent, existing extensive chitin production is to be raw material with discarded shrimp, crab shell basically.In chitin production process, produce a large amount of production wastes that contains protein, calcium chloride, grease and pigment, with coastal manufacturer is example, to produce 1 ton of chitin daily, every day is to the about 1000 tons of sewage of environmental emission (wherein directly wash raw material shrimp, crab shell with seawater about 600 tons, the shrimp of washing behind acid-alkali treatment, crab shell with about 400 tons of fresh water).Undressed production waste dirt is black smelly, if directly discharging can cause the receiving water body eutrophication, also can cause red tide when serious, thereby brings immeasurable loss to aquatic products breed and coastal ecotope.
Sewage water treatment method in the existing chitin production process is generally method of edge treatment.Being about to handle spent picking solution, soda boiling waste liquid, acid wash water, alkaline wash water and place wash-down water thereof etc. behind raw material shrimp, the crab shell is merged into comprehensive wastewater and handles in the lump, but such processing mode makes that the aftertreatment load of sewage is big, and treatment effect is undesirable; In addition because the about 1000mg/L of COD value of seawater itself, and the discharging standards one-level is 100mg/L, and secondary is 150mg/L.After the so many seawater of introducing washs, even the organic impurity in the sewage is all removed (salt that the raw material soda acid in not considering to produce is generated), its water outlet also is difficult to qualified discharge, if the method with reverse osmosis desalination or the dilution of employing fresh water makes the water outlet qualified discharge, the former cost is too high, and general producer is difficult to bear; And the latter generally is difficult to carry out in place coastal or that other Freshwater resources are in short supply with the method that fresh water dilutes, moreover does the total release that still can not reduce COD like this.
In order to have reduced the basic COD value of composite wastewater, people can use fresh water to wash shrimp, crab shell in process of production, but can consume a large amount of fresh water aborning like this.
In addition, the chlorion in the hydrochloric acid introduced of acidleach stage is also very big to the contribution of COD value, specifically is calculated as follows: to produce 1 ton of chitin, needing concentration is 8～8.5 tons of 30% technical hydrochloric acids, if in 8 tons, then wherein contains Cl
-Be 2,334Kg, 1mg Cl in theory
-The oxygen that is equivalent to 0.226mg during by complete oxidation, the absolute CODcr value that promptly enters environment is 527.5Kg.By 300 tons of water displacement, the Cl that introduces in the outlet system
-Concentration 〉=7,780mg/L amounts to CODcr base value 〉=1,758mg/L.Promptly the CODcr base value of Yin Ruing is all more much higher than full sea water.But in the conventional mode of production, be mixed with the impurity such as protein, grease of suitable high density in the spent picking solution, be not easy to reclaim useful matter wherein.
Once more, contain in the soda boiling waste liquid a large amount of protein, grease (emulsification), pigment and salt (with after the acid neutralization wherein saliferous be mainly sodium-chlor), 1 ton of chitin product of every production produces 150～300 kilograms in waste oil, when handling this waste water, generally be neutralized to isoelectric point of protein (acidity) with acid, waste liquid has directly imported composite wastewater after reclaiming protein wherein, and acid has the effect of breakdown of emulsion to oil in water emulsion, so contain oil in water emulsion, dissolving oil and the oil slick (naked eyes as seen when room temperature was high) of a great deal of in the water outlet of post precipitation.Only considered in the method for existing such water of processing that it is the waste water of higher protein content, do not handled and it is used as high oil-containing wastewater, so influenced its treatment effect.
Summary of the invention
Technical problem to be solved by this invention is the sewage water treatment method that provides at above-mentioned prior art present situation in a kind of chitin production process, and waste liquid after treatment can be realized qualified discharge, and can save the fresh water that uses in the production process.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: the sewage water treatment method in a kind of chitin production process, comprise raw materials pretreatment (in case of necessity), acidleach processing and alkali pretreatment stage, reclaim calcium chloride and abraum salt acid in the acidleach treatment process stage, in treating pond, carry out wastewater treatment respectively at each operation stage then, reclaim refuse, the waste water after each operation stage is handled carries out waste water reuse.
Can spent picking solution be distilled in the acidleach treatment process stage, reclaim calcium chloride, acid distilled water and abraum salt acid.
With the waste liquid individual curing in alkali pretreatment stage, its treatment process is the alkaline purification waste liquid through reclaiming protein and after oil removal was handled, its clear liquid was used to wash the shell after alkaline purification.
Described oil removal is handled before protein recovery or in reclaiming or after reclaiming and is carried out.
Described alkaline purification can for soda boiling processing or alkali soak handle or first alkali soak after again soda boiling handle.
The pond body structure of described treating pond is arranged at least two row, each row at least two row, altitudinal gradient is all arranged between each ranks, and the treating pond capacity that is positioned at low level is more than or equal to being positioned at elevated treating pond capacity, and the waste water of high-order treating pond or waste liquid can cause treating pond than its low level by pipeline.
Described treating pond comprises that soda boiling pond, alkali soaking pit, alkaline purification waste liquid storage pond, alkaline purification shell washing pool, acidleach pond, spent picking solution store up the pond, acidity is washed shell water storage pond, comprehensive wastewater pond, acidification pool, anaerobic pond, Aerobic Pond.
More than each same treatment pond at least one, also can be several between equipotential or gradient link to each other.
Compared with prior art, the invention has the advantages that the sewage water treatment method in the chitin production process changed at each operation stage from traditional method of edge treatment and carry out sewage disposal respectively separately, pollutent such as protein in alkali pretreatment stage removal alkaline purification waste liquid, grease, pigment etc., make it not enter the acid leaching process stage, avoided crossed contamination, and be beneficial to the recovery of useful matter in the spent picking solution, solved traditional chitin factory effluent because of high COD value and high chloride content, cause to adopt the difficult problem of conventional way processing such as biochemical process, not only can realize composite wastewater energy qualified discharge, and can make by product obtain reclaiming and effectively utilization; And the waste water after each operation stage processing is carried out waste water reuse, as be used for the washing in raw material pretreatment process section alkali pretreatment stage or acid leaching process stage, can also save employed fresh water greatly; The treating pond structure is arranged at least two row, and each row at least two row all has altitudinal gradient between each ranks, and liquid stream is except that the treating water (liquid) in first initial most significant digit pond like this, and the gravity flow that all the other have all utilized liquid need not pump and takes out, fully save energy.
Description of drawings
Fig. 1 is a process flow sheet of the present invention;
Fig. 2 is the ranking sequential schematic of each treating pond of the present invention, and the direction of arrow among the figure is water (liquid) flow path direction;
Fig. 3 is the structural representation for the treatment of pond of the present invention.
(1) acidleach pond among the figure, (two) spent picking solution storage pond, (three) acidity is washed shell water storage pond, (4) alkaline purification waste liquid storage pond, (five) alkali soaking pit (six) alkaline purification shell washing pool, (seven) comprehensive wastewater pond, (8) acidification pool or anaerobic pond, (nine) Aerobic Pond, (ten) soda boiling pond.
Embodiment
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing.
Embodiment one: the sewage water treatment method in a kind of chitin production process, may further comprise the steps: raw material shrimp shell extruding back water in the comprehensive wastewater equalizing tank is washed with comprehensive wastewater, raw material shrimp shell after the washing is drained in the soda boiling pond and boiled 2 hours with 8% sodium hydroxide solution, shell is separated with alkaline waste liquor, drain, alkaline waste liquor is introduced alkaline purification waste liquid storage pond, transfer the pH value of soda boiling waste liquid to iso-electric point in alkaline purification waste liquid storage pond with acid waste liquid, after reclaiming protein and oil removal processing, clear liquid is introduced alkaline purification shell washing pool, the soda boiling shell washs two to three times (when acid wash water is not enough in alkaline purification shell washing pool, available washing from the beginning) after, wash water precipitates recovery protein with flocculation agent, and the waste water after will handling is then introduced in the equalizing tank of comprehensive wastewater pond; Alkaline purification shell after cleaning is drained the back soaked 6 hours with 3～10% hydrochloric acid solns in the acidleach pond, the acidleach shell is extremely neutral with acid distilled water and tap water washing, promptly obtains the chitin target product after drying.Spent picking solution is stored up spent picking solution in the pond to be handled the back in distillation and reclaims that calcium chloride is made bath water as by product, acid distilled water and the residual salts acid solution is back to acidleach workshop section.Comprehensive wastewater carries out carrying out aerobic treatment, water outlet qualified discharge again after acidifying (or carrying out anaerobism in anaerobic pond) is handled in Aerobic Pond in acidification pool.The pond body structure of above-mentioned various treating ponds is arranged at least two row, each row at least two row, altitudinal gradient is all arranged between each ranks, and the treating pond capacity that is positioned at low level is more than or equal to being positioned at elevated treating pond capacity, and the waste water of high-order treating pond or waste liquid cause treating pond than its low level by pipeline.
Embodiment two: the sewage water treatment method in a kind of chitin production process, may further comprise the steps: raw material shrimp shell was soaked 2 days with 8% sodium hydroxide solution in the alkali soaking pit, shell is separated with alkaline waste liquor, alkaline waste liquor is introduced alkaline purification waste liquid storage pond, soak waste liquid to iso-electric point in alkaline purification waste liquid storage pond with the acidic solution neutralization bases, clear liquid is introduced alkaline purification shell washing pool after oil removal is handled, clear liquid after oil removal is handled and acidity are washed shell water washing alkaline purification back cover two to three times (when wash water is not enough, available washing from the beginning) after, alkali cleaning waste water is introduced the comprehensive wastewater equalizing tank, precipitate recovery protein with flocculation agent in the comprehensive wastewater equalizing tank, the clear liquid after will handling is then introduced in acidification pool or the anaerobic pond; Alkaline purification shell after cleaning is drained the back soaked 4 hours with 5% hydrochloric acid soln in the acidleach pond, the acidleach shell to neutral, promptly obtains the chitin target product with tap water (or acid distilled water) washing after drying.Spent picking solution is introduced in the spent picking solution storage pond.Spent picking solution in the spent picking solution storage pond is introduced to distill in the distiller and is handled back recovery calcium chloride, acid distilled water and residual salts acid solution.Comprehensive wastewater carries out carrying out aerobic treatment, water outlet qualified discharge again after acidifying (or carrying out anaerobism in anaerobic pond) is handled in Aerobic Pond in acidification pool.The pond body structure of above-mentioned various treating ponds is arranged at least two row, each row at least two row, altitudinal gradient is all arranged between each ranks, and the treating pond capacity that is positioned at low level is more than or equal to being positioned at elevated treating pond capacity, and the waste water of high-order treating pond or waste liquid cause treating pond than its low level by pipeline.
Embodiment three: the sewage water treatment method in a kind of chitin production process, may further comprise the steps: raw material shrimp shell was soaked 2 days with 10% sodium hydroxide solution in the alkali soaking pit, shell is separated with alkaline waste liquor, alkaline waste liquor is introduced alkaline purification waste liquid storage pond, soak waste liquid to iso-electric point in alkaline purification waste liquid storage pond with the acidic solution neutralization bases, handle introducing alkaline purification shell washing pool through oil removal, alkali soak shell with acid waste water washing two to three times after, wash water precipitates recovery protein with flocculation agent, and the waste water after will handling is then introduced in the equalizing tank of comprehensive wastewater pond; Alkaline purification shell after cleaning is drained the back soaked 4 hours with 10% hydrochloric acid soln in the acidleach pond, the acidleach shell is extremely neutral with acid distilled water and tap water washing, promptly obtains the chitin target product after drying.Spent picking solution is stored up spent picking solution in the pond to be handled the back in distillation and reclaims that calcium chloride is made bath water as by product, acid distilled water and the residual salts acid solution is back to acidleach workshop section.Comprehensive wastewater carries out carrying out aerobic treatment, water outlet qualified discharge again after acidifying (or carrying out anaerobism in anaerobic pond) is handled in Aerobic Pond in acidification pool.The pond body structure of above-mentioned various treating ponds is arranged at least two row, each row at least two row, altitudinal gradient is all arranged between each ranks, and the treating pond capacity that is positioned at low level is more than or equal to being positioned at elevated treating pond capacity, and the waste water of high-order treating pond or waste liquid cause treating pond than its low level by pipeline.
Embodiment four: the sewage water treatment method in a kind of chitin production process, may further comprise the steps: raw material shrimp shell was boiled 1 hour with 10% sodium hydroxide solution in the alkali soaking pit, shell is separated with alkaline waste liquor, alkaline waste liquor is introduced alkaline purification waste liquid storage pond, soak waste liquid to iso-electric point in alkaline purification waste liquid storage pond with the acidic solution neutralization bases, handle introducing alkaline purification shell washing pool through oil removal, alkali soak shell with acid waste water washing two to three times after, wash water precipitates recovery protein with flocculation agent, and the waste water after will handling is then introduced in the equalizing tank of comprehensive wastewater pond; Alkaline purification shell after cleaning is drained the back soaked 6 hours with 6% hydrochloric acid soln in the acidleach pond, the acidleach shell is extremely neutral with acid distilled water and tap water washing, promptly obtains the chitin target product after drying.Spent picking solution is stored up spent picking solution in the pond to be handled the back in distillation and reclaims that calcium chloride is made bath water as by product, acid distilled water and the residual salts acid solution is back to acidleach workshop section.Comprehensive wastewater carries out carrying out aerobic treatment, water outlet qualified discharge again after acidifying (or carrying out anaerobism in anaerobic pond) is handled in Aerobic Pond in acidification pool.The pond body structure of above-mentioned various treating ponds is arranged at least two row, each row at least two row, altitudinal gradient is all arranged between each ranks, and the treating pond capacity that is positioned at low level is more than or equal to being positioned at elevated treating pond capacity, and the waste water of high-order treating pond or waste liquid cause treating pond than its low level by pipeline.
In the foregoing description, oil removal is handled and can be carried out before protein recovery or in reclaiming or after reclaiming.
Claims (8)
1. the sewage water treatment method in the chitin production process, comprise raw materials pretreatment, acidleach processing and alkali pretreatment stage, it is characterized in that reclaiming calcium chloride and abraum salt acid in the acidleach treatment process stage, in treating pond, carry out wastewater treatment respectively at each operation stage then, reclaim refuse, the waste water after each operation stage is handled carries out waste water reuse.
2. the sewage water treatment method in a kind of chitin production process as claimed in claim 1 is characterized in that in the acidleach treatment process stage spent picking solution being distilled, and reclaims calcium chloride, acid distilled water and abraum salt acid.
3. the sewage water treatment method in a kind of chitin production process as claimed in claim 1, it is characterized in that waste liquid individual curing with the alkali pretreatment stage, its treatment process is the alkaline purification waste liquid through reclaiming protein and after oil removal was handled, its clear liquid was used to wash the shell after alkaline purification.
4. the sewage water treatment method in a kind of chitin production process as claimed in claim 3, it is characterized in that described oil removal is handled before protein recovery or in reclaiming or after reclaiming carries out.
5. the sewage water treatment method in a kind of chitin production process as claimed in claim 3 is characterized in that described alkaline purification is that soda boiling is handled.
6. the sewage water treatment method in a kind of chitin production process as claimed in claim 3 is characterized in that described alkaline purification is that alkali soaks processing.
7. the sewage water treatment method in a kind of chitin production process as claimed in claim 1, the pond body structure that it is characterized in that described treating pond is arranged at least two row, each row at least two row, altitudinal gradient is all arranged between each ranks, the treating pond capacity that is positioned at low level is more than or equal to being positioned at elevated treating pond capacity, and the waste water of high-order treating pond or waste liquid cause treating pond than its low level by pipeline.
8. the sewage water treatment method in a kind of chitin production process as claimed in claim 7 is characterized in that described treating pond comprises that soda boiling pond, alkali soaking pit, alkaline purification waste liquid storage pond, alkaline purification shell washing pool, acidleach pond, spent picking solution store up the pond, acidity is washed shell water storage pond, comprehensive wastewater pond, acidification pool, anaerobic pond, Aerobic Pond.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100499966A CN100402445C (en) | 2005-06-08 | 2005-06-08 | Sewage treating method for chitin production process |
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| CNB2005100499966A CN100402445C (en) | 2005-06-08 | 2005-06-08 | Sewage treating method for chitin production process |
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| CN1709808A CN1709808A (en) | 2005-12-21 |
| CN100402445C true CN100402445C (en) | 2008-07-16 |
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| CNB2005100499966A Expired - Fee Related CN100402445C (en) | 2005-06-08 | 2005-06-08 | Sewage treating method for chitin production process |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101333021B (en) * | 2007-06-27 | 2010-12-01 | 浙江大学宁波理工学院 | Pretreating process of waste water for producing crust element |
| CN100567183C (en) * | 2007-10-26 | 2009-12-09 | 大连利健甲壳素股份有限公司 | The method that chitin, chitosan are produced treating waste liquid |
| CN101215066B (en) * | 2007-12-30 | 2010-06-09 | 浙江大学 | Technique for treating chitin waste water |
| CN104543553A (en) * | 2015-01-04 | 2015-04-29 | 浙江新复大医药化工有限公司 | Method for extracting fly maggot nutrient from chitin production wastewater |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86106726A (en) * | 1986-09-27 | 1988-04-06 | 中国科学院广州化学研究所 | Production of chitin by stepwise acid process |
| CN1321614A (en) * | 2000-10-17 | 2001-11-14 | 陈启松 | Technique for treating waste water from production of chitin |
| CN1467227A (en) * | 2002-07-09 | 2004-01-14 | 邵建华 | Closed path circulation and comprehensive utilization for waste liquor of chitin and derivative production |
-
2005
- 2005-06-08 CN CNB2005100499966A patent/CN100402445C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86106726A (en) * | 1986-09-27 | 1988-04-06 | 中国科学院广州化学研究所 | Production of chitin by stepwise acid process |
| CN1321614A (en) * | 2000-10-17 | 2001-11-14 | 陈启松 | Technique for treating waste water from production of chitin |
| CN1467227A (en) * | 2002-07-09 | 2004-01-14 | 邵建华 | Closed path circulation and comprehensive utilization for waste liquor of chitin and derivative production |
Non-Patent Citations (4)
| Title |
|---|
| 生化法处理甲壳素生产废水. 张亚男等.辽宁城乡环境科技，第18卷第2期. 1998 |
| 生化法处理甲壳素生产废水. 张亚男等.辽宁城乡环境科技，第18卷第2期. 1998 * |
| 甲壳素生产高浓度有机废水的处理回用. 吴春野等.环境导报，第3期. 1999 |
| 甲壳素生产高浓度有机废水的处理回用. 吴春野等.环境导报，第3期. 1999 * |
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